Azodyestuffs insoluble in water and process of making same



substituents.

Patented Feb. 20, 1934 AZODYESTUFFS INSOLUBLE IN WATER AND PROCESS OF MAKING SAME Leopold Laska and Arthur Zitscher, Offenbachont he-Main, Germany, assignors to General Amhne Works Inc., New York, N. Y., a corporation of Delaware No Drawing. Application May 3, 1929, Serial No. 360,308, and in Germany May 7, 1928 16 Claims.

The present invention relates to valuable azodyestufis insoluble in water and to a process of preparing them.

We have found that valuable azodyestuffs insoluble in water are obtained by combining any diaZo-, tetrazoor diazoazo compound with a 4-(2'-hydroxy-3-naphthoyl amino) diphenylamine compound, none of these components containing sulfonic or carboxylic acid groups.

The new dyestufis correspond to the general formula wherein R means an aromatic radical which may contain further arylazo groups and the benzene nuclei may be substituted by other monovalent They may be produced in substance and yield when mixed with the usual substrata valuable color lakes, or they may be prepared on the fiber and yield dyeings and printings of an excellent'fastness especially to light. The shades vary from claret red to black, among which mainly the dark brownish red and brown shadesare a valuable complement in the series of the ice-colors, being fasterto light than hitherto obtainable in those shades by means of the known combinations of this group of the dye-' stufis.

Especially remarkable and surprising is the fact that the dyeings produced from these arylides and tetrazotized dianisidine and aftertreated with copper compounds exhibit a iastness to light surpassing strongly that of the hitherto known dyestuffs prepared from this tetrazo compound and 2-hydroXy-3-naphthoyl-arylamines.

The 4-(2'- hydroxy 3' naphthoylamino) -di phenylamine compounds are unknown hithertoand may be prepared for instance according to the process described in U. S. Patent No. 1,101,111.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade de- Example 1 Well boiled and dried cotton yarn is impregnated with a solution containing per liter '7 grs of 4 (2' hydroxy 3' naphthoyl-amino) diphenylamine, 14 cc. of a caustic soda solution of 34 B. and 14 cc. of Turkey red oil, with further addition of 7 cc. of formaldehyde of 33% strength. Then the'yarn is well wrung out and developed with a diazo solution containing per liter 1.42 grs; of 6-chloro-2-amino-toluene and being neutralized with sodium acetate and thereafter rinsed and soaped. In this manner a brownish red dyeing of a very good fastness to light is obtained. The dyestuff thus produced on the'fiber corresponds to the formula:

4- (2' -hydroxy-3 -naphthoyl-amino) -4 '-nitrodiphenylamine yields when developed with the "same diazo compound a brown dyeing of a likely good fastness to light.

Example 2 Cotton material previously treatedlin the cus-,

brown dyeing of a very good fastness to light is obtained. The dyestuff thus produced on the fiber corresponds to the formula:

to light. The dyestufi thus produced on the fiber corresponds to the formula:

N=N OzN O OH:

OOH

0H. OCH:

O OHa gotton yarn previously treated in an approw 4-.(2-hydroxy-3-naphth0y1amin0)-dipriate manner is impregnated as described in phenylamine is replaced in this example by the Example 1 and then well wrung out. Thereafter Corresponding Y Compound fast it is developed with a tetrazo solution neutralized fu1-1 dark im fi f igz l g f f ifgf g with bicarbonate and containing per liter 2.44 5 93:22 3 g a l zg are g g grs. of dianisidine. Then it is well rinsed. The l With gther diazo tetrazo or diazoazo yarn thus dyed is boiled for half an hour in a solution containing per liter 2 grs of con er "ulpounds and Wlth other 442 hydroxy 3 naphp thoyl-amion) diphenylamine compounds our fate and 2 cc. of acetic acid of 50% strength. process may be carried out likewise Then 1S llnsed and p The following table gives the shades of a num- In s manner a da blue dy m is tai d. ber of dyestufis obtained according to this indistinguished by a very good fastness especially vention:

Diazocompound of Combined with Shade Meta-xylidine 4-(2-hydroxy-3-naphthoyl-amino)-diphenylamine Garnet. 4-chloro-2-to1uidine. D0 Brownish dark red. 5-chloro-2-toluidine Brownish dark red. 5-nitro-2-toluidine- Dark reddish brown. 5-nitro-2-anisidine Deep garnet. Ortho-amino-azo-toluene.. Brown garnet. a-aminoanthraquinone Reddish brown. Para nitrobenzene azo para amino -hydro- Black.

quinone-dimethyl ether. Meta-chloro-aniline Orange brown. 4-chloro-2-amino-l-ethy1-benzene. 1 Orange brown. Meta-nitraniline. Brown. 2-chloro-4-nitraniline Dark brown. Ortho-phenetole-azo D Black. Meta-chloroaniline 4-(2-hydroxy-3 Reddish brown. 4-chloro-2-amino-dip Do Brownish red. Ortho-nitraniline. D0 Reddish brown. Meta xylidine 4-(2-hydroxy-3'-naphthoyl-amino)-4-methoxy dipheny1amine. Dark red like claret. Meta-nitr D Orange brown. 5-nitro-2-anisidine Do Brown garnet. Meta-chloroaniline 4-(2-hydroxy-3-naphthcyl-amino)-3-chloro diphenylamine Reddish brown. 4-chloro-2- Do Brownish red. Ortho-nitraniline Reddish brown. 5-nitro-2-toluidine Garnet. 4-nitro-2-enisidine" D0 Dark red like claret. 5-nitro-2-t0luidine 4-(2'-hydroxy-3-naphthoy1amin0)3.4-dichl0ro diphenylamine. Brownish red. 5-nitro-2-anisidine D0 Bluish red like claret. 2.5-dichIoro-aniline 4-(2-hydroxy-3-naphthoyl-amino)-4-nitro-diphenylamine Reddish brown. G-chloro-Z-toluidine--. Do Reddish brown. 4-chloro-2-nitraniline. Reddish brown. 4.6-dichloro-3-to1uidine Reddish brown. Metra-nitraniline Do Brown. zx-arnino-anthraquinone D Reddish brown.

We wish it to be understood that in the followthoy1-amino)-dipheny1amine compound of the ing claims the term combining means everygeneral mu Where combining in substance or on a substratum 14G especially on the fiber and that the term diazo compound comprises all diazotized aromatic amino compounds including such as contain already a diazo or azo group.

We claim:

1. A process which comprises combining any diazo compound of the benzene, naphthalene or anthracene series with a 4-(2-hydroxy-3-naphwherein the benzene nuclei may contain alkyl, 14.5 alkoxy, halogen or nitro, substituents, none of these components containing sulfonic or carboxylic acid groups.

alkoxy, halogen or nitro, substituents.

2. A process which comprises combining any diazo compound of the benzene, naphthalene or anthracene series not containing sulfonic or carboxylic acid groups with 4-(2-hydroxy-3-naph- 7. The azodyestuffs of the general formula:

thoyl-amino) -diphenylamine of the formula: 89

3. A process which comprises combining the tetrazo compound of dianisidine with a 4-(2-hy- OOH: droxy-3-naphthoyl-amino) -diphenylamine com- 90 pound of the general formula:

. O NH not contaimng sulfonic 0r carboxyhc acid groups,

wherein the benzene nuclei of the arylido -radicals may be substituted by alkyl, alkoxy, halogen or nitro, substituents, which dyestuffs are when dry dark powders insoluble in water, yielding when mixed with the usual substrata valuable color lakes and when produced on the fiber and aftertreated thereon with a copper compound dark blue dyeings of a good fastness especially to light.

wherein the benzene nuclei may contain alkyl,

4. A process which comprises combining the tetrazo compound of dianisidine with 4-(2-hydroxy-3-naphthoyl amino) diphenylamine of the formula:

8. The azo dyestufi of the formula:

5. The azodyestuffs of the general formula: -on

OCH: RN=N not containing sulfonic or carboxylic acid groups, wherein It means an aromatic radical of the group consisting of radicals of the benzene, naphthalene and anthracene series which may contain further aryl azo groups and the benzene nuclei may be substituted by alkyl, alkoxy, halogen or nitro, substituents, which compounds are when dry claret red to black colored powders, insoluble in water, yielding when mixed with the usual substrata valuable color lakes and when produced on the fiber dyeings and printings of a good fastness espewhich dyestuff is when dry a dark powder, insoluble in water, yielding when mixed with the usual substrata valuable color lakes and when produced on the fiber and aftertreated thereon with a copper compound dark blue dyeings of a cially to light. good fastness especially to light. 135

6. The azodyestuffs of the general formula: 9. The azo dyestuff of the following formula:

RN=N

[ OCH:

not containing sulfonic or carboxylic acid groups, wherein R means an aromatic radical of the group consisting of radicals of the benzene, naphthalene and anthracene series which may contain further aryl azo groups, which compounds are when dry claret red to black colored powders, insoluble in water, yielding when mixed with the usual substrata valuable color lakes and when produced on the fiber dyeings and printings of a good fastness especially to light.

I OH

l4? which dyestuff is when dry a black powder, in-

soluble in water, yielding when mixed with the usual substrata valuable color lakes and when produced on the fiber black dyeings of a good fastness especially to light. I50

10. The azo dyestufi? of the following formula: which dyestuff is when dry a dark powder, in-

soluble in water, yielding when mixed with the usual substrata valuable color lakes and when I produced on the fiber brown garnet dyeings of '5 v HS 1 a good fastness especially to light.

11. Fiber dyed with the azodyestuffs of claim 5, 12. Fiber dyed with the azodyestufis of claim 6,

c0- 13. Fiber dyed with the azodye tuffs of claim 7,

14. Fiber dyed with the azodyestuff of claim 8,

ll NHQNH-O 15. Fiber dyed with the azo dyestuff as claimed l in claim 9.

16. Fiber dyed with the azo dyestufi as claimed in claim 10.

LEOPOLD LASKA. i; ARTH R ZI HER.-

70 led 

